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Since inorganic nanoparticles have unique properties that differ from those of bulk materials, their material applications have attracted attention in various fields. In order to utilize inorganic nanoparticles for functional materials, they must be dispersed without agglomeration. Therefore, the surfaces of inorganic nanoparticles are typically modified with organic ligands to improve their dispersibility. Nevertheless, the relationship between the tail group structure in organic ligands and the dispersibility of inorganic nanoparticles in organic solvents remains poorly understood. We previously developed amphiphilic ligands that consist of ethylene glycol chains and alkyl chains to disperse inorganic nanoparticles in a variety of organic solvents. However, the structural requirements for amphiphilic ligands to "flexibly" disperse nanoparticles in less polar to polar solvents are still unclear. Here, we designed and synthesized several phosphonic acid ligands for structure-function relationship studies of flexdispersion. Dynamic light scattering analysis and visible light transmittance measurements revealed that the ratio of alkyl/ethylene glycol chains in organic ligands alone does not determine the dispersibility of the nanoparticles in organic solvents, but the arrangement of the individual chains also has an effect. From a practical application standpoint, it is preferable to design ligands with ethylene glycol chains on the outside relative to the particle surface.
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Novel p-coumaric acid microemulsion systems were developed to circumvent its absorption and bioavailability challenges. Simplex-lattice mixture design and machine learning methods were employed for optimization. Two optimized formulations were characterized using in vitro re-dispersibility and cytotoxicity on various tumor cell lines (MCF-7, CaCO2, and HepG2). The in vivo bioavailability profiles of the drug loaded in the two microemulsion systems and in the suspension form were compared. The optimized microemulsions composed of Labrafil M1944 CS (5.67%)/Tween 80 (38.71%)/Labrasol (38.71%)/water (16.92%) and Capryol 90 (0.50%)/Transcutol P (26.67%)/Tween 80 (26.67%)/Labrasol (26.67%)/water (19.50%), respectively. They revealed uniform and stable p-coumaric acid-loaded microemulsion systems with a droplet size diameter of about 10 nm. The loaded microemulsion formulations enhanced the drug re-dispersibility in contrast to the drug suspension which exhibited 5 min lag time. The loaded formulae were significantly more cytotoxic on all cell lines by 11.98-16.56 folds on MCF-7 and CaCo2 cells and 47.82-98.79 folds on HepG2 cells higher than the pure drug. The optimized microemulsions were 1.5-1.8 times more bioavailable than the drug suspension. The developed p-coumaric acid microemulsion systems could be considered a successful remedy for diverse types of cancer.
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Ácidos Cumáricos , Aprendizado de Máquina , Polissorbatos , Humanos , Células CACO-2 , ÁguaRESUMO
The plastic production that contributes to the global plastic reservoir presents a major challenge for society in managing plastic waste and mitigating the environmental damage of microplastic (MP) pollution. In the environment, the formation of biomolecular corona around MPs enhance the stability of MP suspensions, influencing the bioavailability and toxicity of MPs. Essential physical properties including MP stability, dispersibility, agglomeration, and dimensional size must be precisely defined and measured in complex media taking into account the formation of a protein corona. Using static multiple light scattering (SMLS), small angle X-ray scattering (SAXS), Raman microscopy, and scanning electron microscopy (SEM), we measured the particle size, density, stability, and agglomeration state of polyethylene and polypropylene MPs stabilized in aqueous suspension by BSA. SEM analysis revealed the formation of nanoplastic debris as MP suspensions aged. Our results suggest that protein adsorption favors the formation of secondary nanoplastics, potentially posing an additional threat to ecosystems. This approach provides analytical methodologies by integrating SEM, SMLS, and SAXS, for characterizing MP suspensions and highlights the effect of the protein corona on size measurements of micro/nanoplastics. Our analysis demonstrates the detectability of secondary nanoplastics by SEM, paving the way for monitoring and controlling human exposure.
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Hydrothermal pretreatment is useful for microfibrillated cellulose (MFC) preparation due to its safety, but the remaining hemicellulose might affect MFC properties. This study aimed to investigate the effect of centrifugation time on hemicellulose removal and the physicochemical properties of MFC obtained after hydrothermal pretreatment and micro-fibrillation. In this study, centrifugation was applied to the MFC suspension at varying duration times. Composition analysis and Fourier transform infrared spectra indicated that fractionated MFC has no hemicellulose content after 10, 20, and 30 min centrifugation. It also showed an approximately 5 times higher than 0.5 % g/g of initial solid concentration, indicated by a lower gel concentration point, than unfractionated MFC. Scanning electron microscope images of the fractionated MFC for 30 min (MFC2C) presented thin, long cellulose fibrils of 517 nm in average diameter and 635-10,000 nm in length that induced a slower sedimentation rate. MFC2C dispersion was also improved by autoclave sterilization by regulating cellulose structure, rheology, and crystallinity. As a result, MFC dispersibility can be enhanced by removing hemicellulose through simple centrifugation.
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Celulose , Algas Comestíveis , Rodófitas , Celulose/químicaRESUMO
The affinity between carbon nanotubes (CNTs) and organic compounds is of substantial importance since it strongly relates to the dispersibility of CNTs in those compounds. Several affinity evaluation methods have been developed so far, and the concept of the Hansen solubility parameter is a representative method widely used in the field of nanocarbon materials. Here, we demonstrate that CNT-loaded silica columns can effectively assess the affinity of organic compounds for CNT surface by exploiting the chromatographic retention time as a criterion. Obtained trends of the affinity of organic compounds for CNT were compared to those based on Hansen solubility parameter distance values. Most organic compounds showed similar trends, but one exceptional compound was observed. Simple CNT dispersion tests were conducted with these organic compounds to demonstrate the advantage of the chromatographic assessment. Further, we conducted comparison experiments using a pyrene-functionalized column and other CNT-loaded columns to elucidate the characteristics of each CNT column. The chromatographic approaches using CNT columns would be beneficial for realizing CNT suspensions with improved CNT dispersibility.
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Graphene has achieved mass production via various preparative routes and demonstrated its uniqueness in many application fields for its intrinsically high electron mobility and thermal conductivity. However, graphene faces limitations in assembling macroscopic structures because of its hydrophobic property. Therefore, balancing high crystal quality and good aqueous dispersibility is of great importance in practical applications. Herein, we propose a tape-wrapping strategy to electrochemically fabricate water-dispersible graphene (w-Gr) with both excellent dispersibility (~4.5 mg/mL, stable over 2 months), and well-preserved crystalline structure. A large production rate (4.5 mg/min, six times faster than previous electrochemical methods), high yield (65.4% ≤5 atomic layers) and good processability are demonstrated. A mechanism investigation indicates that the rational design of anode configuration to ensure proper oxidation, deep exfoliation and unobstructed mass transfer is responsible for the high efficiency of this strategy. This simple yet efficient electrochemical method is expected to promote the scalable preparation and applications of graphene.
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Curdlan, a natural polysaccharide, exhibits emulsion-stabilizing and viscosity-modifying properties. However, when employed solely in the aqueous phase, curdlan's adhesive nature impedes droplet dispersion, resulting in a gel-like structure with limited applicability. This investigation formulated a biphasic stabilized oil-in-water emulsion by supplementing the oil phase with beeswax and the aqueous phase with curdlan and soy protein isolate (SPI). The addition of SPI transformed the structural characteristics from a gel-like to a mayonnaise-like structure. Maximal electrostatic repulsion was observed at an internal phase volume fraction of 30%, effectively precluding droplet aggregation owing to the absolute zeta potentials surpassing 40 mV. The emulsions displayed shear-thinning rheological behavior, with a higher storage modulus than the loss modulus, indicative of favorable elastic properties. Molecular docking revealed the predominant role of polar amino acids in facilitating hydrogen bond formation. This study provides a template for developing emulsions with biphasic stability and desirable dispersibility.
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Emulsões , Reologia , Proteínas de Soja , Água , beta-Glucanas , Emulsões/química , beta-Glucanas/química , Proteínas de Soja/química , Água/química , Viscosidade , Simulação de Acoplamento Molecular , Tamanho da Partícula , Óleos/química , Ligação de HidrogênioRESUMO
Tungsten oxide (WO3) is known for its photochromic properties, making it useful for smart windows, displays, and sensors. However, its small bandgap leads to rapid recombination of electron-hole pairs, resulting in poor photochromic performance. This study aims to enhance the photochromic properties of WO3 by synthesizing hexagonal tungsten oxide via hydrothermal synthesis, which increases surface area and internal hydrates. Titanium oxide (TiO2) was adsorbed onto the tungsten oxide to inject additional charges and reduce electron-hole recombination. Additionally, polyvinylpyrrolidone (PVP) was used to improve dispersion in organic solvents, allowing for the fabrication of high-quality films using the doctor blade method. Characterization confirmed the enhanced surface area, crystal structure, and dispersion stability. Reflectance and transmittance measurements demonstrated significant improvements in photochromic properties due to the composite structure. These findings suggest that the introduction of TiO2 and PVP to tungsten oxide effectively enhances its photochromic performance, broadening its applicability in various advanced photochromic applications.
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Covalent triazine frameworks (CTFs) have recently emerged as an efficient class of photocatalysts due to their structural diversity and excellent stability. Nevertheless, the synthetic reactions of CTFs have usually suffered from poor reversibility, resulting in a low crystallinity of the materials. Here, we report the introduction of methoxy groups on the monomer 2,5-diphenylthiazolo[5,4-d]thiazole to reinforce interlayer π-π interactions of the resulting donor-acceptor type CTFs, which improved crystallinity, further increasing the visible light absorption range and allowing for efficient separation and transport of carriers. The morphology is strongly correlated to the wettability, which has a significant impact on the mass transfer capacity and photocatalytic activity in the photocatalytic reaction. To further improve crystallinity and photocatalytic activity, CTF-NWU-T3 photocatalysts in a bowl shape were prepared using a SiO2 template. The energy band structure, photocatalytic hydrogen evolution, and pollutant degradation efficiency of involved materials were investigated. The donor-acceptor type CTF-NWU-T3 with a bowl-shaped morphology, synthesized using the template method and the introduction of methoxy groups, exhibited an excellent photocatalytic hydrogen production rate of 32064 µmol·h-1·g-1. This study highlights the significance of improving donor-acceptor interactions and increasing the dispersibility of catalyst particles in dispersion to enhance the photocatalytic activity of heterogeneous photocatalysts.
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The inherent large number of hydroxyl groups of silica poses strong hydrophilicity, resulting in poor dispersibility in the natural rubber matrix. Here, the silica's surface was hydrophobically modified with [3-(triethoxysiliconyl) propyl] tetrasulfide (Si69) to improve the dispersibility and reinforce the mechanical properties of silica/natural rubber composites. The structure and morphology of modified silica were characterized by Fourier infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray electron spectroscopy (XPS), nuclear magnetic resonance spectroscopy and the contact angle. Further, the mechanical properties, dynamic mechanical properties and morphology of silica/natural rubber composites were studied with a universal electronic tension machine, dynamic thermal mechanical properties analyzer (DMA) and scanning electron microscope (SEM). The experimental results show that the Si69 was successfully grafted onto the surface of silica, thereby significantly improving the water contact angle (a 158.6% increase) and enhancing the mechanical properties of modified silica/natural rubber composites.
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The goal of this work was to develop acrylonitrile-butadiene (NBR) elastomer composites filled with hydroxyapatite (HAP) characterized by improved cure characteristics and resistance to burning. Silane, i.e., (3-aminopropyl)-triethoxysilane, ionic liquid, i.e., 1-decyl-3-methylimidazolium bromide and surfactant, i.e., cetyltrimethylammonium bromide, were used to improve the filler's dispersibility in the elastomer matrix and to reduce the time and temperature of vulcanization. The effects of HAP and dispersants on the cure characteristics, crosslink density and physico-chemical properties of NBR composites were explored. The additives used, especially the ionic liquid and surfactant, effectively improved the dispersion of HAP in the NBR matrix. The amount of HAP and the dispersant used strongly affected the cure characteristics and crosslink density of NBR. The optimal vulcanization time significantly increased with HAP content and was pronouncedly reduced when ionic liquid and surfactant were applied. In addition, ionic liquid and surfactant significantly lowered the onset vulcanization temperature and improved the crosslink density and hardness of the vulcanizates while impairing their elasticity. HAP and dispersants did not significantly affect the damping properties or chemical resistance of NBR vulcanizates. Above all, application of HAP considerably enhanced the resistance of vulcanizates to thermo-oxidative aging and reduced their flammability compared with the unfilled NBR.
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The aim of this study was to investigate how the propensity for aerosolisation in binary adhesive mixtures was affected by the drug load, and to determine whether these findings could be linked to different blend states. Binary blends of two different lactose carriers, each with varying size and morphology, were prepared together with budesonide. In vitro aerosolisation studies were conducted at four different pressure drops, ranging from 0.5 to 4 kPa, utilising a Next Generation Impactor. Several dispersion parameters were derived from the relationship between the quantity of dispersed API and the pressure drop. The evolution of the parameters with drug load was complex, especially at low drug loads. While similar responses were observed for both carriers, the range of drug load that could be used varied significantly. The choice of carrier not only influenced the capacity for drug loading but also affected the spatial distribution of the API within the mixture, which, in turn, affected its aerosolisation propensity. Thus, the drug dispersion process could be linked to different configurations of the lactose carrier and budesonide in the blends, i.e. blend states. In conclusion, the study suggests that the concept of blend states can provide an explanation for the complex dispersion process observed in adhesive blends.
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Adesivos , Aerossóis , Budesonida , Portadores de Fármacos , Lactose , Budesonida/química , Budesonida/administração & dosagem , Lactose/química , Administração por Inalação , Adesivos/química , Portadores de Fármacos/química , Tamanho da Partícula , Química Farmacêutica/métodosRESUMO
This study investigates the effect of different mixers and the applicability of the mixing energy (ME) concept to dry powder formulations for inhalation. With the aim to step-wise build and expand this concept, adhesive mixtures of 2 % budesonide and lactose carrier were investigated, both with 1 % magnesium stearate (MgSt) added in a 'coating' step, and without, the latter referred to as 'naked' formulations. For high shear mixed formulations, the fine particle fraction (FPF) was found to increase with increasing ME up to 60 % and thereafter decreased, using the Novolizer device. The data could be well fitted to the modeling equation, thus confirming the validity of the ME concept. The naked formulations displayed a linear decrease in FPF with increasing ME, again showing the validity of the ME concept. For Turbula mixed formulations, FPF increased with increased mixing time (and mixing energy) for all batches. The naked (binary) composition reached to higher FPF values than for high shear mixing and the formulation with MgSt reached to FPF values around 60 %, demonstrating that it is possible to achieve the same high drug dispersibility with the Turbula mixer as for high shear mixer. An equation for calculation of mixing energy in Turbula mixing was set up in an analogous way to the equation for high shear mixing, which enabled direct comparison between the two mixers.